Co-existence of distinct supramolecular assemblies in solution and in the solid state

The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G-quartet based assemblies are formed in chloroform depending on the nature of the cation, anion and salt concentration, as characterized by circular dichroism and time course diffusion-ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G-quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon-like assemblies as revealed by fast magic-angle spinning (MAS) NMR spectroscopy. Distinct N-H∙∙∙N and N-H∙∙∙O intermolecular hydrogen bonding interactions drive quartet and ribbon-like self-assembly resulting in markedly different 2D 1H solid-state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible - further demonstrating the changes that occur in the self-assembly process of a lipophilic nucleoside upon a solid-state to solution-state transition and vice versa. A systematic study for complexation with different cations (K+, Sr2+) and anions (picrate, ethanoate and iodide) emphasises that the existence of a stable solution or solid-state structure may not reflect the stability of the same supramolecular entity in another phase

GaceC10 infrared spectrum O=C1C(N=CN2[C@@]3([H])[C@@](OC(C)(C)O4)([H])[C@@]4([H])[C@](COC(CCCCCCCCC)=O)([H])O3)=C2N=C(N)N1

Infrared spectrum solid state acquired with diamond ATR attachment of "GaceC10" sample I-AH-1<div>SMILES O=C1C(N=CN2[C@@]3([H])[C@@](OC(C)(C)O4)([H])[C@@]4([H])[C@](COC(CCCCCCCCC)=O)([H])O3)=C2N=C(N)N1</div><div><p> 2',3'-<i>O</i>-Isopropylidene-5'-decanoylguanosine    </p><div><br></div></div

Data for Co-existence of distinct supramolecular assemblies in solution and in the solid state

The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G-quartet based assemblies are formed in chloroform depending on the nature of the cation, anion and salt concentration, as characterized by circular dichroism and time course diffusion-ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G-quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon-like assemblies as revealed by fast magic-angle spinning (MAS) NMR spectroscopy. Distinct N-H∙∙∙N and N-H∙∙∙O intermolecular hydrogen bonding interactions drive quartet and ribbon-like self-assembly resulting in markedly different 2D 1H solid-state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible - further demonstrating the changes that occur in the self-assembly process of a lipophilic nucleoside upon a solid-state to solution-state transition and vice versa. A systematic study for complexation with different cations (K+, Sr2+) and anions (picrate, ethanoate and iodide) emphasises that the existence of a stable solution or solid-state structure may not reflect the stability of the same supramolecular entity in another phase